Stannous phenylcatecholates



Patented July 4, 1950' Firestone Tire & Rubber Company, Akron, hio,a corporati0n=of0hi0 I NoDrawing. :App licationJanuary 10, 1948, Serial No. 51,674

2 Claims. (cram-429) if'iliis lnvention relates to the :use 'ofstannous drtho and para-phenylcatecholates asstabilizers for rubbers.

lie' -word catechol is usedherein to refer EXAMPLE Stcmnous p-phenylcatecholate g Thirty-seven grams of ,3,4-dihydroxydiphenyl to 'nrtho-dihydroxybenzene sometimes 'called 5 i v. .p-phenylcatechol) was dissolved 1n 50 per cent "p-ymcatechm' The i g fif ethyl alcohol, and a solution of 45.2 grams of called salts because 1 De d vstannous chloride dihydrate in alcohol was added. salts. They may be basic salts or hy ra es. ey the resultingsolution, a solution of 16 grams "mayfeven be Werner COOTdmated chelate'wm' of sodium hydroxide in .200 ml of 50 er cent 82 2; fig 1t Seems more probable that alcohol-water 'was added slowly during stirring y The precipitate was filtered and then washed Although Stannous 4-phenyl?atechlate (span' successively with 100 m1. portions of per cent nous para-phenylcatecholate) 1s a preferred staethyl alcoh 01 ethyl alcohol and Water It was bilizer of this invention, other stannous phenylaibdriedandfovndto Weigh 51 grams n h at catecholates are included as, for example: l5 mg it decomposed before melting hf f Stannous 4-phenyl-6-chlorocatecholate calculated t =4 ;g found m stannous 4"PhenY1'6tertbutylcatecholate This stabilizer was-tested against phenyl-betastannous Chlorophenyn Catecholate naphthylamine by adding small'amountsoi'each E g f g 1 t 'to latex resulting from the copolymerization of stannous er y eny ca ee 0 e 1,3-butadiene and styrene in the proportions to v stannous 4-tert-octy1-G-phenylcatecholate give thecopolymerknown as Thejlatices :Stannous=4+chloro-6-phenylcatecholate I f stannous 4 bromo 6 pheny1catecho1ate were coagulated dried and aged. The products stannous 4+Phenyl-G-tert-amylcatecholate r W m ally tedetermlne wh e w Stannous 4 pheny1 5 bromocatecho1ate 2o fication or other deterioration had set 1n; The sb 4 1 t t .results of the tests arerecorded in the' 'followlng Stannous 4-pheny1-6-n0rma1-decyl catecholate table.

TABLE I After Drying 20 Hours at C. After aging 4 daysat C. After aging 1 day at 0.

Stabilizer Color Hand Test Color Hand Test Color i I Hand Test 1% stannous p-phenylcate- Light cream- No deterioration VerylighthrowmJNo deterioratiom. Light brown Slightly set up. 2 73 lsttisnnons p-phenylcatedo do do do (1n ,7 Do. I 1 7?, gh elg l-beta-napthylaminefl Brown do Brow do Brow Qo igiderably set 2% phenyl-beta-napthylamine. do r a do Darkbrom Do.

These stabilizers include stannous salts of ortho- 40 The above data'show that thetest material dis- "andpara' phenvlcatecholates substituted in either colors rless'ithan-the cqmmerplal h i n; ring with halogen or any alkyl group containing g -F' gq g g g g llflz up to twentyor more carbon atoms, and thus ina; g igg g gigtf g zg m 9 an pom clude dodecyl, octadecyl, etc.,1n either ring. 45 :In: another test in whichgcoagu-yla cofitaimngiz 'TThfollowing illustrates one method of preparmg the compounds 2 :,per cent of; each stabilizer were dried and then :zoven-agedat 90 C., the results were:

Oven-Aging Alter Drying 20 hours at 75 O. Stabilizer 2 Days 4 Days 7 Color "Condition Condition Condition S tannous p-phenylcatecholate l Li g h 1; gt a y 4 No deterioration Slightly setup. Slightly setup green.

Phenyl-beta-naphthylamine Brow Considerahljs'etfflp- ,Qured.

The samples of Table I were coagulated with purified aluminum sulfate, and those of Table II were coagulated with commercial aluminum sulfate. Both tests show the test stabilizer discolors 4 Thus, the stabilizers of this invention are e1 fective in rubbery copolymers of a conjugateddiene monomer and a vinyl monomer. The conjugated-diene monomers include, for example,

less than the commercial stabilizer and also i 5 1,3-butadiene, isoprene, 2-cyanobutadiene-1,3, gives improved protection to the copolymer. "cyclopentadiene, piperylene, dimethylbutadieneh p lymer coagula containi 2 P Cent 1,3, 2-methy1butadiene-l,3, etc. The vinyl mono- Of e esp Stabilizers were COmDOHIIded mers include, for example, aromatic monomers accordin to the foll win form l I such as, for example, styrene, alpha methylsty- Parts by weight rene, nuclearly substituted styrenes, monochloro- Copolymer containing 2% stabilizer 100.0 styrene, dichlorostyrene, vinylnaphthalene, vinyl- Coal tar plasticizer 3.0 "'biphenyl, vinylcarbazole, etc. and aliphatic Pine tar 3.0 monomers such as, for example, acrylonitrile, Stearic acid I. 3.0 methacrylonitrile, alpha-chloracrylonitrile,acryl- Zinc oxide 5. amide, acrylic-acid alkyl esters in which the alkyl Accelerator 1.2 radical contains one to five carbon atoms,,a1kyl- Channel black acrylic ketones in which the alkyl group contains Sulfur one to five carbon atoms, etc. l The stocks were Cured for 40, 60, 80 and 120 9 The stabilizer may be used with other stabilizutes at F. some of the cured stocks were ers. It may be used in amounts ranging from 0.1 aged 4 days in an oven at 212 F. The physical to pe C e invention is defined in the properties of the stocks were then determined. claimsl Iii-Table III, for each property average values Whatlclaim is: for the four cures are presented. 1. Stannous salts of the class consisting of TABLE III 2007 Modulus Tensile Stren th Elongation at g Break- Stabilizer Normal Aged Normal Aged Normal Aged stannous p-phenylcatecho- '12 455 1,455 2,785 2, 840 685 250 phenyl-beta-naphthylamine.. 580 1,605 2, 885 2,570 585 300 (Modulus and tensile strength are measured herein in pounds per square inch.)

The stock containing the test material compares favorably with that containing the commercial stabilizer.

phenylcatecholates, unsubstituted, halogen-substituted, and substituted with an alkyl group of not over twenty carbon atoms.

40 Stocks simllarly compounded from 0 1 3 2. Stannous para-phenylcatecholate. containing 2 per cent of the different stabilizers 1 were cured and aged 10 hours in an air bomb at HARRY ALBERT. 260 F. under pounds air pressure. The following tests show the results of such aging:

TABLE IV 200% Modulus Tensilestrength g gg Stabilizer Normal Aged Normal Aged. Normal Aged stannous p-phenylcatecholate 455 1, 350 2,785 2, 625 685 381) phenyl-beta-nuphthylamineh 580 1,540 2,885 2, 630 585 335 The test stock proved about equal to that containing the commercial stabilizer, in tensile and elongation retention, and slightly superior from the standpoint of modulus increase.

In testing the stabilizers in a rubber-like butadiene-l,3-acrylonitrile copolymer (composed of per cent butadiene and 30 per cent acrylonitrile), 2 per cent of each stabilizer was added to latex resulting from the copolymerization. The latex was coagulated; The coagula were dried and aged 4 days at C. The following table records the results:

TABLE V 001023111 gondition Color alter er gmg Stabilizer Drying I Color Condition stannousp-phenylcatecholate- White. Tan Good. phenyl-beta-naplithylaminei. Lightbrown Brown Do.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Weinland et al.: Zeit. anorg. allgem. Chem,

vol. (1926) pp. '12, 79. 

1. STANNOUS SALTS OF THE CLASS CONSISTING OF PHENYLCATECHOLATES, UNSUBSTITUTED, HALOGEN-SUBSTITUTED, AND SUBSTITUTED WITH AN ALKYL GROUP OF NOT OVER TWENTY CARBON ATOMS. 